Methods of treating hardening oil before use by adding a mixture of ethoxylated acyclic compounds and film-forming acyclic compounds

ABSTRACT

A mixture consisting of ethoxylated acyclic compounds as emulsifiers, acyclic compounds as film-forming agents and possibly antioxidants and corrosion inhibitors, is added to a mineral-oil based hardening oil.

United States Patent Lindstedt 1 June 10, 1975 METHODS OF TREATINGHARDENING OIL [56] References Cited BEFORE USE BY ADDING A MIXTURE OFUNITED STATES PATENTS ETHOXYLATED ACYCLIC COMPOUNDS 3,192,165 6/1965Fields et a1, 252/79 AND FILM-FORMING ACYCLIC 3,224,910 12/1965 McEwen148/143 COMPOUNDS 3,281,288 10/1966 Carver et a1..... 148/20.6 3,340,1939/1967 Fields et al. 252/79 [75] Inventor: Per Olof Lindstedt, Molndal,

Sweden Primary ExaminerWalter R. Satterfield [73] Assignee: OlofLindstedt & Co. AB, Molndal,

Sweden [57] ABSTRACT [22] Filed: Feb 20, 1974 A mixture consisting ofetl oxylated acyclic compounds as emulsifiers, acyclic compounds asfilm- [21] App]. No.: 444,223 forming agents and possibly antioxidantsand corrosion inhibitors, is added to a mineral-oil based harden- 52 US.Cl. 148/29; 252/73; 252/77; mg

252/79 5 Claims, N0 Drawings [51] Int. Cl B23k 35/24 [58] Field ofSearch 148/29, 28, 27, 143, 20,6,

METHODS OF TREATING HARDENING OIL BEFORE USE BY ADDING A MIXTURE OFETHOXYLATED ACYCLIC COMPOUNDS AND FILM-FORMING ACYCLIC COMPOUNDS The useof liquids for the hardening of metals is well known. For example,metallic objects can be cooled rapidly by immersing them in water oroil. Immersion in oil often produces a milder and a more even effectsince the occurrence of stress within the material is avoided.

The oils used must be stable at the temperatures in question and oftenparaffinor naphthene-based mineral oils or mixtures thereof are used, ifdesired with additives included.

After the immersion the oil should be removed from the metal surface.This can be done by alkaline washing or by treatment with solvents, suchas chlorinated hydrocarbons. Another possibility is to add an emulsifierto the hardening oil. In that case the oil after hardening is removedfrom the material by flushing with water.

The emulsifiers used in the latter case must possess a high emulsifyingcapacity and be thermostable so that no decomposition products arecreated which could have an injurious effect on the surface of themetal. The emulsifiers must also be relatively insensitive to thehardness and pH of the water, so that immersion or spraying with waterdoes not result in precipitations which could be harmful to the metalsurface.

From the point of view of environmental preservation it is importantthat the emulsifiers chosen can be decomposed biologically, so that theyare incapable of causing any damage.

It has been found that certain ethoxylated acyclic compounds, viz.ester, alkyl ether, fatty acid amide and alkylamine-ethylene oxideadducts, satisfy the abovementioned requirements. Such acyclic compoundscontain 8-20 C-atoms in straight or branched alkyl chains which can besaturated or unsaturated, or mixtures thereof, and at least one activeH-atom. The fol lowing are suitable compounds:

a. Fatty acids containing 10-20 C-atoms.

b. Alkanols, primary or secondary, such as cetyl alcohol, oleyl/cetylalcohol, tridecyl alcohol, C -C alkanols, C -C alkanols, etc.

0. Carboxylic acid amides, such as palmitic acidmono or diethanolamide,oleic acidlauric acidmonoor diethanol-amide, etc.

d. Primary, secondary or tertiary alkyl amines and alkylpolyamines,'such as lauryl amine, lauryl oleyl amine, tallow amine,tallow propylene diamine, etc.

After the building up of ethylene oxide these products contain 2-15,preferably 2-8, ethylene oxide units in the hydrophilic part.

It is of the utmost importance that a thin film be left on the surfaceof the metal after the removal of the hardening oil. In order to achievethis a compound which is, in itself, neither soluble in nor dispersibleby water, is added to the oil, in addition to the emulsifier. In orderto make this film adhere well to the metal surface it should contain oneor more OH, -CONI-l or NH -groups. This oil film protects the surfaceagainst corrosion.

An addition of this type to the hardening oil acts also as solubilizerfor the ethoxylated emulsifier, thereby ensuring a better distributionof the latter in the mineral oil.

Suitable film-forming additives are acyclic compounds or mixturesthereof with straight or branched, saturated or partially saturatedalkyl chains containing 10-26 C-atoms and at least one polar group, suchas Ol-l, CONH or NH -groups.

Suitable compounds are: fatty acid esters, cetyl oleyl alcohol, tridecylalcohol, stearyl alcohol, alkanols with 10-16 C-atoms, lauric acidmono-ethanolamide, lauryl amine, tallow amine, tallow diamine, etc.

It is advisable to mix the emulsifier with the filmforming additivebefore adding it to the mineral oil. In this case suitable mixingproportions are: 60-95 percent ethoxylated acyclic compounds and 40-5percent film-forming additives. This mixture is added to the oil in anamount of 1-10 percent, preferably 2-5 percent, by weight of the oil. I

Also other additions may prove appropriate. Thus, the addition of anantioxidant, such as dibutyl phenol or dibutylmethyl phenol, may beconsidered. The addition ratio is approximately 0.5-] percent by weightof the oil.

In certain cases the addition ofa corrosion inhibitor may also berequired. An acyclic amine compound containing 10-20 C-atoms, such ascetylamine or lauryl diamine, can be used for this purpose, the additionratio being 0.5-1 .5 percent by weight of the oil.

The invention will be illustrated by the following Examples in which twomineral oils were used, i.e. one paraffin-based oil with 2.1 E/50Cviscosity and one naphthene-based oil with 7.5 E/50C viscosity.

The mineral oils were mixed with an emulsifier or an emulsifier mixturein the proportion 97:3 percent by weight. The mineral oil containing theemulsifier or emulsifier mixture was then mixed with water in theproportion 5 parts by weight of mineral oil emulsifier to parts byweight of water.

In certain cases, the mineral oil emulsifier or emulsifier mixture were,before mixing, heated for 18 hours up to C. After the emulsifier-bearingmineral oil had been mixed with water, the emulsion was left to standfor one-half hour, after which the surface creaming was measured; it isstated as a percentage of the emulsion.

A very important factor is the solubility of the emulsifier, oremulsifier mixture, in the mineral oil. In order to arrive at a good,even emulsification and, above all, a long storage life, the emulsifieror emulsifier mixture should be clearly dissolved in the mineral oil. Toallow comparison of the results obtained, the content of the emulsifieror emulsifier mixture in the mineral oil was at all times maintained at3 percent by weight.

EXAMPLE 1 97 Parts by weight of a paraffin-based oil were mixed with 3parts by weight of an emulsifier mixture containing 90 percent laurylalcohol polyglycol ether with 3 mols of ethylene oxide per mol of laurylalcohol, and 10 percent 50/55 oleyl/cetyl alcohol. A clear andtranslucent oil mixture was obtained. After mixing the emulsion,creaming amounted to 3-4 percent after one-half h.

With another, identically composed sample a heat resistance test wascarried out; after formation of the emulsion this oil has showed 3-4percent creaming after one-half h. Thus, the emulsifying capacity of theoil mixture was not reduced by heating it for 18 h to For purposes ofcomparison an ethoxylated nonyl phenol of the same proportions asmentioned above containing 6 mols of ethylene oxide was added to theparaffin-based oil. This mixture was, however, cloudy, unlike thepreceding one which was completely clear. Cloudiness means, as has beenalready mentioned, that there is a great risk that the emulsion willseparate under storage.

As regards the emulsifying capacity both before and after heating, whichwas carried out in the same way as mentioned above, creaming amounted to3-4 percent in both cases.

EXAMPLE 2 3 Parts by weight of an emulsifier mixture containing EXAMPLE3 3 Parts by weight of an emulsifier mixture containing 90 percentlauryl alcohol polyglycol ether with 3 mols of ethylene oxide per mol oflauryl alcohol and 10 percent coconut fatty acid diethanolamide wereadded to 97 parts by weight of paraffin-based oil. The emulsifiermixture dissolved completely clearly in the paraffinbased oil. Theemulsifying capacity was the same as was mentioned in the precedingExamples.

EXAMPLE 4 97 Parts by weight of a paraffin-based oil were mixed with 3parts by weight of an emulsifier mixture containing 90 percent oleylamine polyglycol ether with 7 mols of ethylene oxide per mol of oleylamine and 10 percent 50/55 oleyl/cetyl alcohol. The emulsifier mixturedissolved clearly in the mineral oil.

EXAMPLE 5 97 Parts by weight of a naphthene-based oil were mixed with 3parts by weight of an emulsifier mixture containing 90 percent laurylalcohol polyglycol ether with 3 mols of ethylene oxide per mol of laurylalcohol and 10 percent oleyl/cetyl alcohol.

The oil mixture dissolved completely clearly in the mineral oil. As wasmentioned in Example 1, the emulsifying capacity was tested first withthe abovementioned oil mixture per se and secondly with theabovementioned oil mixture heated for 18 h to 180C. In both cases theemulsions indicated l-2 percent creaming after one-half h.

For purposes of comparison, a nonyl phenol polyglycol ether containing 6mols of ethylene oxide per mol of nonyl phenol was used as an emulsifieralso in this case. This product, in the proportions 97 parts by weightnaphthene-based oil to 3 parts by weight emulsifier, was not clearlysoluble in the mineral oil. The

emulsifying capacity, tested as described previously,

was 1-2 percent both before and after heating.

EXAMPLE 6 97 Parts by weight of a naphthene-based oil were added to 3parts by weight of an emulsifier mixture containing 90 percent laurylalcohol polyglycol ether 1 with 3 mols of ethylene oxide per mol oflauryl alcohol and 10 percent coconut fatty acid diethanol amide. Theproduct dissolved clearly in the naphthene-based oil, and had the sameemulsifying capacity as the emulsifier mixture mentioned in Example 5.

EXAMPLE 7 97 Parts by weight of a paraffih-based oil were mixed with 3parts by weight of an emulsifier mixture containing 90 percent oleylcetyl polyglycol ether with 5 mols of ethylene oxide per mol ofoleyl/cetyl alcohol and 10 percent of a fatty alcohol mixture with 20 ormore C- atoms in the alkyl group. The emulsifier mixture dissolvedalmost clearly in the oil. A 5 percent emulsion indicated.4.5 percentcreaming one-halfh after mixing and One-half h after heat treatment.

The same test carried out with naphthene-based oil gave a clear solutionof the emulsifier mixture in the mineral oil and the emulsion indicated2 percent creaming before and after heat treatment.

Thus, the emulsifying capacity was'not impaired either in paraffin-basedor naphthene-based oil.

EXAMPLE 8 97 Parts by weight of paraffin-based oil were mixed with 3parts by weight of an emulsifier mixture containing 79 percent tallowdiamine polyglycol ether with 3 mols of ethylene oxide per mol of tallowdiamine,,20 percent oleyl/cetyl alcohol, 1 percent tallow diamine as acorrosion inhibitor. The emulsifier mixture was clearly soluble in themineral oil and gave a fine emulsion. After one-half h before and afterheating creaming amounted to 3 percent.

The same test in the naphthene-based oil gave a clear solution of theemulsifier mixture in the mineral oil, a fine emulsion, and 1 percentcream before and after heating.

Thus, the emulsifying capacity showed no change either in paraffin-basedor in naphthene-based oil.

EXAMPLE 9 97 Parts by Weight of paraffin-based oil were mixed with 3parts by weight of an emulsifier mixture containing percent ethoxylatedoleic acid diethanolamide with 10 mols of ethylene oxide per mol ofoleic acid diethanolamide and 30 percent oleyl/cetyl alcohol. Theemulsifier mixture was clearly soluble in the oil and resulted in rapidemulsion, and the emulsion produced 5 percent cream oil before and afterheating.

The test with the same emulsifier mixture in naphtheme-based oil gave anopaque solution of the emulsifier-in the oil and the emulsion produced 4percent cream oil before and after heating.

The emulsifying capacity of the mixture was inferior to that of thepreceding examples; the heating, however, did not result in anydeterioration.

EXAMPLE 1O 97 Parts by weight of paraffin-based oil were mixed with 3parts of an emulsifier mixture containing 88 percent lauryl alcoholpolyglycol ether, 10 percent oleyl/- cetyl alcohol and 2 percent stearylamine. The emulsifier mixture dissolved clearly in the mineral oil andthe emulsion produced, before heating, 4.5 percent cream oil and, afterheating, 5 percent cream.

The same emulsifier mixture in naphthene-based oil gave a clear solutionand the emulsion produced, before and after heating, 3.5 percent cream.

EXAMPLE 1 l 97 Parts by weight of paraffin-based oil were mixed with 3parts of an emulsifier mixture containing 90 percent ethoxylated coconutfatty acid monoethanolamide with 2 mols of ethylene oxide per mol ofcoconut fatty acid mono-ethanolamide and percent olive oil. Theemulsifier mixture dissolved almost clearly in the oil, gave a fineemulsion and produced, before and after heating, 4.5 percent cream.

The same emulsifier mixture was almost clearly soluble innaphthene-based oil and the emulsion indicated before and after heating3.5 percent creaming.

EXAMPLE 12 97 Parts by weight of naphthene-based oil were mixed with 3parts by weight of an emulsifier mixture containing 67 percent oleicacid polyglycol ester and 33 percent oleyl amine. The oleic acidpolyglycol ester contained 6 mols of ethylene oxide per mol of oleicacid. The emulsifier mixture dissolved opaquely in the oil and theemulsion indicated, before heating, 2 percent and, after heating, 2.5percent creaming.

EXAMPLE 13 97 Parts by weight of paraffin-based oil were mixed with 3parts by weight of an emulsifier mixture containing 67 percent oleicacid polyglycol ester with 6 mols of ethylene oxide per mol of oleicacid and 33 percent coconut fatty diamine. The emulsifier mixturedissolved opaquely in the oil and gave a fine emulsion indicating,before heating, 4 percent and, after heating, 4.5 percent creaming.

EXAMPLE 14 97 Parts by weight of paraffin-based oil containing 1 percentby weight oleyl amine as a corrosion inhibitor were mixed with 3 partsby weight of an emulsifier mixture containing 90 percent oleic acidpolyglycol ester with 6 mols of ethylene oxide per mol of oleic acid and10 percent oleyl/cetyl alcohol. The emulsifier mixture gave an opaquesolution in the mineral oil and a fine emulsion indicating 4.5 percentcreaming before and after heating.

97 Parts by weight of naphthene-based oil containing 1 percent by weightof coconut fatty diamine as a corrosion inhibitor were added to 3 partsby weight of the same emulsifier mixture. The dissolved opaquely in theoil and gave a fine emulsion indicating 2 percent creaming before andafter heating.

Thus, by adding a corrosion inhibitor directly to the oil and byheating, the emulsifying capacity did not deteriorate.

What I claim and desire to secure by Letters Patent l. A method ofimproving a mineral oil-based oil for use in cooling metallic objects byrapidly immersing said objects in said oil, said method comprisingadding to said oil l-lO percent, by weight of said oil, of a mixtureconsisting of:

A. 60-95 percent by weight of an emulsifier, said emulsifier being abiodegradable, ethoxylated, acyclic compound selected from the groupconsisting of esters, alkyl ethers, fatty acid amides andalkylamine-ethylene oxide adducts, wherein said compound contains 8-20carbon atoms in alkyl groups and 2-15 hydrophilic, ethylene oxide units;and

B. 40-5 percent by weight of a C -C film-forming,

acyclic compound selected from the group consisting of esters, alcohols,amides and amines, said film-forming compound being neither soluble innor dispersible by water.

2. A method of improving a mineral oil-based oil for use in coolingmetallic objects by rapidly immersing said objects in said oil, saidmethod comprising adding to said oil 1-10 percent, by weight of saidoil, of a mixture consisting of:

A. 60-95 percent by weight of an emulsifier, said emulsifier being abiodegradable, ethoxylated, acyclic compound selected from the groupconsisting of esters, alkyl ethers, fatty acid amides andalkylamine-ethylene oxide adducts, wherein said compound contains 8-20carbon atoms in alkyl groups and 2-15 hydrophilic, ethylene oxide units;

B. 40-5 percent by weight of a C -C film-forming,

acyclic compound selected from the group consisting of esters, alcohols,amides and amines, said film-forming compound being neither soluble innor dispersible by water; and

C. an antioxidant selected from the group consisting of dibutyl phenoland dibutyl methyl phenol.

3. A method of improving a mineral oil-based oil for use in coolingmetallic objects by rapidly immersing said objects in said oil, saidmethod comprising adding to said oil l-lO percent, by weight of saidoil, of a mixture consisting of:

A. 60-95 percent by weight of an emulsifier, said emulsifier being abiodegradable, ethoxylated, acyclic compound selected from the groupconsisting of esters, alkyl ethers, fatty acid amides andalkylamine-ethylene oxide adducts, wherein said compound contains 8-20carbon atoms in alkyl groups and 2-15 hydrophilic, ethylene oxide units;

B. 40-5 percent by weight of a C -C film-forming,

acyclic compound selected from the group consisting of esters, alcohols,amides and amines, said film-forming compound being neither soluble innor dispersible by water;

C. an antioxidant selected from the group consisting of dibutyl phenoland dibutyl methyl phenol; and

D. a corrosion inhibitor selected from the group consisting of C -Cacyclic amines.

4. A method of improving a mineral oil-based oil for use in coolingmetallic objects by rapidly immersing said objects in said oil, saidmethod comprising adding to said oil 2-5 percent by weight of said oil,of a mixture consisting of:

A. 60-95 percent by weight of an emulsifier, said emulsifier being abiodegradable, ethoxylated, acyclic compound selected from the groupconsisting of esters, alkyl ethers, fatty acid amides andalkylamine-ethylene oxide adducts, wherein said compound contains 8-20carbon atoms in alkyl groups and 2-l5 hydrophilic, ethylene oxide units;and

B. 40-5 percent by weight of a C -C film-forming,

acyclic compound selected from the group consisting of esters, alcohols,amides and amines, said of esters, alkyl ethers, fatty acid amides andalkylamine-ethylene oxide adducts, wherein said compound contains 8-20carbon atoms in alkyl groups and 2-8 hydrophilic, ethylene oxide units;and

B. 405 percent by weight of a C -C film-forming,

acyclic compound selected from the group consisting of esters, alcohols,amides and amines, said film-forming compound being neither soluble 'innor dispersible by water.

1. A METHOD OF IMPROVING A MINERAL OIL-BASED OIL FOR USE IN COOLINGMETALLIC OBJECTS BY RAPIDLY IMMERSING SAID OBJECTS IN SAID OIL, SAIDMETHOD COMPRISING ADDING TO SAID OIL 1-10 PERCENT, BY WEIGHT OF SAIDOIL, OF A MIXTURE CONSISTING OF: A. 60-95 PERCENT BY WEIGHT OF ANEMULSIFIER, SAID EMULSIFIER BEING A BIODEGRADABLE, ETHOXYLATED, ACYCLICCOMPOUND SELECTED FROM THE GROUP CONSISTING OF ESTERS, ALKYL ETHERS,FATTY ACID AMIDES AND ALKYLAMINE-ETHYLENE OXIDE ADDUCTS, WHEREIN SAIDCOMPOUND CONTAINS 8-20 CARBON ATOMS IN ALKYL GROUPS AND 2-15HYDROPHILIC, ETHYLENE OXIDE UNITS, AND B. 40-5 PERCENT BY WEIGHT OF AC10-C26, FILM-FORMING, ACYCLIC COMPOUND SELECTED FROM THE GROUPCONSITING OF ESTERS, ALCOHOLS, AMIDES AND AMINES, SAID FILM-FORMINGCOMPOUND BEING NEITHER SOLUBLE IN NOR DISPERSIBLE BY WATER.
 2. A methodof improving a mineral oil-based oil for use in cooling metallic objectsby rapidly immersing said objects in said oil, said method comprisingadding to said oil 1-10 percent, by weight of said oil, of a mixtureconsisting of: A. 60-95 percent by weight of an emulsifier, saidemulsifier being a biodegradable, ethoxylated, acyclic compound selectedfrom the group consisting of esters, alkyl ethers, fatty acid amides andalkylamine-ethylene oxide adducts, wherein said compound contains 8-20carbon atoms in alkyl groups and 2-15 hydrophilic, ethylene oxide units;B. 40-5 percent by weight of a C10-C26, film-forming, acyclic compoundselected from the group consisting of esters, alcohols, amides andamines, said film-forming compound being neither soluble in nordispersible by water; and C. an antioxidant selected from the groupconsisting of dibutyl phenol and dibutyl methyl phenol.
 3. A method ofimproving a mineral oil-based oil for use in cooling metallic objects byrapidly immersing said objects in said oil, said method comprisingadding to said oil 1-10 percent, by weight of said oil, of a mixtureconsisting of: A. 60-95 percent by weight of an emulsifier, saidemulsifier being a biodegradable, ethoxylated, acyclic compound selectedfrom the group consisting of esters, alkyl ethers, fatty acid amides andalkylamine-ethylene oxide adducts, wherein said compound contains 8-20carbon atoms in alkyl groups and 2-15 hydrophilic, ethylene oxide units;B. 40-5 percent by weight of a C10-C26, film-forming, acyclic compoundselected from the group consisting of esters, alcohols, amides andamines, said film-forming compound being neither soluble in nordispersible by water; C. an antioxidant selected from the groupconsisting of dibutyl phenol and dibutyl methyl phenol; and D. acorrosion inhibitor selected from the group consisting of C10-C20acyclic amines.
 4. A method of improving a mineral oil-based oil for usein cooling metallic objects by rapidly immersing said objects in saidoil, said method comprising adding to said oil 2-5 percenT by weight ofsaid oil, of a mixture consisting of: A. 60-95 percent by weight of anemulsifier, said emulsifier being a biodegradable, ethoxylated, acycliccompound selected from the group consisting of esters, alkyl ethers,fatty acid amides and alkylamine-ethylene oxide adducts, wherein saidcompound contains 8-20 carbon atoms in alkyl groups and 2-15hydrophilic, ethylene oxide units; and B. 40-5 percent by weight of aC10-C26, film-forming, acyclic compound selected from the groupconsisting of esters, alcohols, amides and amines, said film-formingcompound being neither soluble in nor dispersible by water.
 5. A methodof improving a mineral oil-based oil for use in cooling metallic objectsby rapidly immersing said objects in said oil, said method comprisingadding to said oil 1-10 percent, by weight of said oil, of a mixtureconsisting of: A. 60-95 percent by weight of an emulsifier, saidemulsifier being a biodegradable, ethoxylated, acyclic compound selectedfrom the group consisting of esters, alkyl ethers, fatty acid amides andalkylamine-ethylene oxide adducts, wherein said compound contains 8-20carbon atoms in alkyl groups and 2-8 hydrophilic, ethylene oxide units;and B. 40-5 percent by weight of a C10-C26, film-forming, acycliccompound selected from the group consisting of esters, alcohols, amidesand amines, said film-forming compound being neither soluble in nordispersible by water.